Radiation-sensitive resin composition

Abstract

A radiation-sensitive resin composition comprising (A) a resin which comprises at least one recurring unit (I-1), (I-2), or (I-3), and a recurring unit (II), and is insoluble or scarcely soluble in alkali, but becomes alkali soluble by action of an acid, (B) a photoacid generator, and (C) a polycyclic compound. The resin composition is used as a chemically-amplified resist for microfabrication utilizing deep UV rays.

1 . A radiation-sensitive resin composition comprising: 
 (A) a resin which comprises at least one recurring unit selected from the group consisting of recurring units (I-1), (I-2), and (I-3) shown by the following formula (1), and a recurring unit (II) shown by the following formula (2), and is insoluble or scarcely soluble in alkali, but becomes alkali soluble by action of an acid,                          wherein R 1 , R 3 , and R 5  individually represent a hydrogen atom or a methyl group, and R 2 , R 4 , and R 6  individually represent a hydrogen atom or a linear or branched alkyl group having 1-4 carbon atoms, X represents a methylene group, an oxygen atom, or a sulfur atom, and a is an integer of 1-5,                          wherein R 7  represents a hydrogen atom or a methyl group, R 8 s individually represent a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1-4 carbon atoms, provided that at least one R 8  represents a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or two R 8 s form, in combination with the carbon atom to which the two R 8 s bond, a divalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, with the remaining R 8  being a linear or branched alkyl group having 1-4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof;    (B) a photoacid generator; and    (C) a polycyclic compound which has a molecular weight of 1,000 or less and includes a group —COOR 9 , wherein R 9  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms.    
   
   
       2 . The radiation-sensitive resin composition according to  claim 1 , wherein at least one recurring unit selected from the group consisting of the recurring units (I-1), (I-2), and (I-3) shown by the formula (1) is the recurring unit (I-1).  
   
   
       3 . The radiation-sensitive resin composition according to  claim 1 , wherein the group —COOC(R 8 ) 3  in the recurring unit (II) is at least one group selected from the group consisting of a t-butoxycarbonyl group and groups of the following formulas (i-1), (i-2), (i-10), (i-11), (i-13), (i-14), (i-16), (i-17), (i-34), (i-35), (i-40), (i-41), (i-43), (i-47), (i-48), and (i-49).  
     
       
         
         
             
             
         
       
       
         
         
             
             
         
       
       
         
         
             
             
         
       
     
   
   
       4 . The radiation-sensitive resin composition according to  claim 1 , wherein the resin (A) further comprises at least one recurring unit other than the recurring units (I-1), (I-2), (I-3), and (II).  
   
   
       5 . The radiation-sensitive resin composition according to  claim 1 , wherein the photoacid generator (B) is at least one compound selected from the group consisting of onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds.  
   
   
       6 . The radiation-sensitive resin composition according to  claim 1 , wherein the amount of the photoacid generator (B) is 1-20 parts by weight for 100 parts by weight of the resin (A).  
   
   
       7 . The radiation-sensitive resin composition according to  claim 1 , wherein the polycyclic compound (C) is at least one compound selected from the group consisting of compounds shown by the following formulas (4) to (9):  
     
       
         
         
             
             
         
       
     
     wherein R 9  represents a hydrogen atom, a substituted or linear or branched alkyl group having 1-20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms;  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4), Z represents a hydrocarbon group with a valence of m which has a polycyclic carbon ring in which the number of carbon atoms which make up the ring is 6-20 or a derivative thereof, and m is an integer of 1-4;  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4);  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4), R 11  and R 12  individually represent a hydrogen atom, a linear or branched alkyl group having 1-4 carbon atoms, a linear or branched hydroxyalkyl group having 1-4 carbon atoms, —OR 13 , wherein R 13  represents a hydrogen atom, a linear or branched alkyl group having 1-4 carbon atoms, or —CH 2 COOR 14 , wherein R 14  represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, or —COOR 15 , wherein R 15 , represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, or —CH 2 COOR 16  wherein R 16  represents a hydrogen atom or an alkyl group having 1-18 carbon atoms and n and p are integers of 0-2;  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4) and R 7 , R 8 , R 19 , and R 20  individually represent a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1-4 carbon atoms, or a linear or branched alkoxyl group having 1-4 carbon atoms;  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4), and R 21 , R 22 , and R 23  individually represent a hydrogen atom or a hydroxyl group, provided that at least one of R 21 , R 22 , and R 23  represents a hydroxyl group.  
   
   
       8 . The radiation-sensitive resin composition according to  claim 1 , wherein the polycyclic compound (C) is the compound shown by the following formula (9),  
     
       
         
         
             
             
         
       
     
     wherein R 9  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, and R 21 , R 22  and R 23  individually represent a hydrogen atom or a hydroxyl group, provided that at least one of R 21 , R 22  and R 23  represents a hydroxyl group.  
   
   
       9 . A radiation-sensitive resin composition comprising: 
 (A) a resin which comprises at least one recurring unit selected from the group consisting of recurring units (I-1), (I-2), and (I-3) shown by the following formula (1), and a recurring unit (II) shown by the following formula (2), and is insoluble or scarcely soluble in alkali, but becomes alkali soluble by action of an acid,                          wherein R 1 , R 3 , and R 5  individually represent a hydrogen atom or a methyl group, and R 2 , R 4 , and R 6  individually represent a hydrogen atom or a linear or branched alkyl group having 1-4 carbon atoms, X represents a methylene group, an oxygen atom, or a sulfur atom, and a is an integer of 1-5,                          wherein R 7  represents a hydrogen atom or a methyl group, each R 8  individually represents a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1-4 carbon atoms, provided that at least one R 8  represents a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or two R 8 s form, in combination with the carbon atom to which the two R 8 s bond, a divalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, with the remaining R 11  being a linear or branched alkyl group having 1-4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof;    (B) a photoacid generator; and    (C) a polycyclic compound which has a molecular weight of 1,000 or less and includes a group —COOR 9 , wherein R 9  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms; and wherein the group —COOC(R 8 ) 3  in the recurring unit (II) is at least one group selected from the group consisting of a t-butoxycarbonyl group and a group represented by the formulae (i-1), (i-2), (i-10), (i-11), (i-14), (i-16), (i-17), (i-34), (i-35), (i-40), (i-41), (i-47), (i-48) and (i-49),                                                              
   
   
       10 . The radiation-sensitive resin composition according to  claim 9 , wherein at least one recurring unit selected from the group consisting of the recurring units (I-1), (I-2), and (I-3) shown by the formula (1) is the recurring unit (I-1).  
   
   
       11 . The radiation-sensitive resin composition according to  claim 9 , wherein the resin (A) further comprises at least one recurring unit other than the recurring units (I-1), (I-2), (I-3), and (II).  
   
   
       12 . The radiation-sensitive resin composition according to  claim 9 , wherein the photoacid generator (B) is at least one compound selected from the group consisting of onium salt compounds, halogen-containing compounds, diazoketone compounds, sulfone compounds, and sulfonic acid compounds.  
   
   
       13 . The radiation-sensitive resin composition according to  claim 9 , wherein the amount of the photoacid generator (B) is 1-20 parts by weight for 100 parts by weight of the resin (A).  
   
   
       14 . The radiation-sensitive resin composition according to  claim 9 , wherein the polycyclic compound (C) is at least one compound selected from the group consisting of compounds shown by the following formulae (4) to (9):  
     
       
         
         
             
             
         
       
     
     wherein R 9  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms;  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4), Z represents a hydrocarbon group with a valence of m which has a polycyclic carbon ring in which the number of carbon atoms which make up the ring is 6-20 or a derivative thereof, and m is an integer of 1-4;  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4);  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4) and R 11  and R 12  individually represent a hydrogen atom, a linear or branched alkyl group having 1-4 carbon atoms, a linear or branched hydroxyalkyl group having 1-4 carbon atoms, —OR 3 , wherein R 13  represents a hydrogen atom, a linear or branched alkyl group having 1-4 carbon atoms, or —CH 2 COOR 14 , wherein R 14  represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, or —COOR 5 , wherein R 15 , represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, or —CH 2 COOR 16 , wherein R 16  represents a hydrogen atom or an alkyl group having 1-18 carbon atoms, and n and p are integers of 0-2;  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4) and R 17 , R 18 , R 19 , and R 20  individually represent a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1-4 carbon atoms, or a linear or branched alkoxyl group having 1-4 carbon atoms;  
     
       
         
         
             
             
         
       
     
     wherein R 9  is the same as defined for the formula (4), and R 21 , R 22 , and R 23  individually represent a hydrogen atom or a hydroxyl group, provided that at least one of R 21 , R 22 , and R 23  represents a hydroxyl group.  
   
   
       15 . The radiation-sensitive resin composition according to  claim 9 , wherein the polycyclic compound (C) is the compound shown by the following formula (9),  
     
       
         
         
             
             
         
       
     
     wherein R 9  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, and R 21 , R 22  and R 23  individually represent a hydrogen atom or a hydroxyl group, provided that at least one of R 21 , R 22  and R 23  represents a hydroxyl group.  
   
   
       16 . A radiation-sensitive resin composition comprising: 
 (A) a resin which comprises at least one recurring unit selected from the group consisting of recurring units (I-1), (I-2), and (I-3) shown by the following formula (1), and a recurring unit (II) shown by the following formula (2), and is insoluble or scarcely soluble in alkali, but becomes alkali soluble by action of an acid,                          wherein R 1 , R 3 , and R 5  individually represent a hydrogen atom or a methyl group, and R 2 , R 4 , and R 6  individually represent a hydrogen atom or a linear or branched alkyl group having 1-4 carbon atoms, X represents a methylene group, an oxygen atom, or a sulfur atom, and a is an integer of 1-5,                          wherein R 7  represents a hydrogen atom or a methyl group, each R 8  individually represents a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1-4 carbon atoms, provided that at least one R 8  represents a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or two R 8 s form, in combination with the carbon atom to which the two R 8 s bond, a divalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, with the remaining R 8  being a linear or branched alkyl group having 1-4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof;    (B) a photoacid generator; and    (C) a polycyclic compound selected from the group consisting of compounds shown by the following formulae (4) to (8):                          wherein R 9  represents a hydrogen atom, a substituted or linear or branched alkyl group having 1-20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms;                          wherein R 9  is the same as defined for the formula (4), Z represents a hydrocarbon group with a valence of m which has a polycyclic carbon ring in which the number of carbon atoms which make up the ring is 6-20 or a derivative thereof, and m is an integer of 1-4;                          wherein R 9  is the same as defined for the formula (4);                          wherein R 9  is the same as defined for the formula (4) and R 11  and R 12  individually represent a hydrogen atom, a linear or branched alkyl group having 1-4 carbon atoms, a linear or branched hydroxyalkyl group having 1-4 carbon atoms, —OR 13 , wherein R 13  represents a hydrogen atom, a linear or branched alkyl group having 1-4 carbon atoms, or —CH 2 COOR 14  wherein R 14  represents a hydrogen atom or an alkyl group having 1-4 carbon atoms, or —COOR 5 , wherein R 15 , represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1-20 carbon atoms, or —CH 2 COOR 16 , wherein R 16  represents a hydrogen atom or an alkyl group having 1-18 carbon atoms, and n and p are integers of 0-2;                          wherein R 9  is the same as defined for the formula (4) and R 17 , R 18 , R 19 , and R 20  individually represent a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1-4 carbon atoms, or a linear or branched alkoxyl group having 1-4 carbon atoms.    
   
   
       17 . A radiation-sensitive resin composition comprising: 
 (A) a resin which comprises at least one recurring unit selected from the group consisting of recurring units (I-1), (I-2), and (I-3) shown by the following formula (1), and a recurring unit (II) shown by the following formula (2), and is insoluble or scarcely soluble in alkali, but becomes alkali soluble by action of an acid,                          wherein R 1 , R 3 , and R 5  individually represent a hydrogen atom or a methyl group, and R 2 , R 4 , and R 6  individually represent a hydrogen atom or a linear or branched alkyl group having 1-4 carbon atoms, X represents a methylene group, an oxygen atom, or a sulfur atom, and a is an integer of 1-5,                          wherein R 7  represents a hydrogen atom or a methyl group, R 8 s individually represent a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1-4 carbon atoms, provided that at least one R 8  represents a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or two R 8 s form, in combination with the carbon atom to which the two R 8 s bond, a divalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, with the remaining R 11  being a linear or branched alkyl group having 1-4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof;    (B) a photoacid generator; and    (C) a polycyclic compound shown by the following formula 9,                          wherein R 9  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, and R 21  and R 22  represent a hydroxyl group and R 23  represents a hydrogen atom, or R 21  represents a hydroxyl group and R 22  and R 23  represent a hydrogen atom.    
   
   
       18 . A radiation-sensitive resin composition comprising: 
 (A) a resin which comprises at least one recurring unit selected from the group consisting of recurring units (I-1), (I-2), and (I-3) shown by the following formula (1), and a recurring unit (II) shown by the following formula (2), and is insoluble or scarcely soluble in alkali, but becomes alkali soluble by action of an acid,                          wherein R 1 , R 3  and R 5  individually represent a hydrogen atom or a methyl group, and R 2 , R 4 , and R 6  individually represent a hydrogen atom or a linear or branched alkyl group having 1-4 carbon atoms, X represents a methylene group, an oxygen atom, or a sulfur atom, and a is an integer of 1-5,                          wherein R 7  represents a hydrogen atom or a methyl group, R 8 s individually represent a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1-4 carbon atoms, provided that at least one R 8  represents a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, or two R 8 s form, in combination with the carbon atom to which the two R 8 s bond, a divalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof, with the remaining R 8  being a linear or branched alkyl group having 1-4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4-20 carbon atoms or a derivative thereof;    (B) a photoacid generator; and    (C) a polycyclic compound shown by the following formula 9,                          wherein R 9  represents a hydrogen atom, a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, or —CH 2 COOR 10 , wherein R 10  represents a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1-20 carbon atoms, or a substituted or unsubstituted monovalent alicyclic hydrocarbon group having 3-20 carbon atoms, and R 21 , R 22 , and R 23  individually represent a hydrogen atom or a hydroxyl group, provided that at least one of R 21 , R 22 , and R 23  represents a hydroxyl group.